US2805254A

US2805254A - Process for the preparation of primary amines

Info

Publication number: US2805254A
Application number: US482917A
Authority: US
Inventors: Bernard H Nicolaisen
Original assignee: Olin Corp
Current assignee: Olin Corp
Priority date: 1955-01-20
Filing date: 1955-01-20
Publication date: 1957-09-03
Anticipated expiration: 1974-09-03

Description

Sept. 3, 1957 B. 1-1. NICOLAISEN 2,895,254

PROCESS FOR THE PREPARATION OF PRIMARY AMINES Filed Jan. 20, 1955 6 17 1 2 21 '7 1 9 O COOLER v iXRfl c 11 cL' -A/FRACTIONATING TOWER j NaOH ;-4:

(AQUEOUS) 2a REBOILER c 11 (1\11- -2 HCL +WATER c 1-1 CN 14 5 WATER INVENTOR BERNARD NICOLAISEN azww, Ma fmzw ATTORNEY halide and ammonia from the efiiuent aqueous product bearing solution.

Water is charged to the reaction zone in an amount sutiicient to maintain all of the reaction products in aqueous solution. Suitable holding times are automatically provided in the new method by controlling the product take-oft rate and the reactant charge rate.

The temperatures and pressures which are suitable for use in the new process vary depending upon the aliphatic halide employed in the reaction. Ordinarily, temperatures of about 30 to 40 C. in the upper portion of the reaction zone or fractionating tower and from about 100 to 200 C. inthe' lower portion of the reaction zone 'are suitable. Suitable pressures include those from about atmospheric to about 300 pounds per square inch or more. Y

In a modification of the new process, part of the water charged to the reaction zone maycarry with it a suitable proportion of a solublenon-volatile alkali provided that the alkali is charged to the reaction zone at a point below that at which appreciable quantities of aliphatic halides are present. Although any water soluble non-volatile alkali may be used, sodium hydroxide is preferred because of its low cost and ready availability. Some water is ordinarily charged to the reaction zone at a higher point in order to depress the vapor pressure of ammonia and insure the solution of the amine hydrohalide product. Charging the aqueous alkali to the reaction zone or fractionating tower at a point below that at which substantial amounts of halide are present avoids hydrolysis of the aliphatic halide and converts the amine hydrohalide prodnot and any ammonium halide present to the free amine or ammonia and sodium halide. monia thus liberated is returned to the central portion of the reaction zone as described above.

Water and sodium chloride are of much lower volatility than any of'the other substances present in the system described above and are, therefore, easily removed from the lower portion of the reaction zone as an aqueous solution. .The introduction of alkali produces additional heat in the reaction zone and liberates this heat at the point of maximum usefulness. In the modification of the new process in which no alkali is introduced into the reaction zone, the efiluent aqueous solution contains a primary amine hydrohalidewhich may be neutralized This method wastes the heat of 'neutraliza-' separately. tion. The primary amine product may be removed from the aqueous salt solution, obtained as described above, as an azeotrope with water or as the anhydrous amine by conventional methods.

The process of the present invention is useful for the ammoniation of aliphatic halides where the water azeotrope of the halide to be converted has a boiling point above that of ammonia (-33 C. at standard conditions) and below the boiling point of water. In the modification of the present invention in which a water soluble non-volatile alkali is employed, suitable aliphatic halides are those which form water azeotropes distilling at temperatures below that at which the water azeotrope of the amine corresponding to the halide has a substantial vapor pressure. In other words, alkali may be used only with aliphatic halides whose water azeotropes have relatively low boiling points, whereas in the modification of the present invention in which no alkali is employed, aliphatic halides which form water azeotropes boiling at relatively high temperatures but still below the boiling point of water'may be used since the product is obtained in the form of the relatively less volatile primary amine hydrohalide.

In general then, it is necessary to select aliphatic halide reactants which can be volatilized from an aqueous solution containing the product without volatilizing significant amounts of the product. The product is removed from the reaction zone immediately after formation as an aqueoussolution which is then subjected, in the lower portion of:

The relatively volatile 4 the reaction zone, to a temperature sufficiently high to remove dissolved aliphatic halide from the solution. In this way, contact of product and reactants is kept to a minimum and the formation of undesirable by-products such as secondary and tertiary amines and the like is minimized.

Aliphatic halides which are suitable for use in the modification of the process of this invention in which a water soluble non-volatile alkali is employed to obtain an aqueous primary amine solution as a bottoms product include methyl chloride, ethyl chloride, and ethylene dichloride and the like. The water azeotropes of the aliphatic halides of this category have boiling points which are sufliciently lower than those of the water azeotropes of the corresponding primary amines to make separation of the reactant halide from the aqueous product bearing solution relatively easy. Temperatures in the reaction zone are generally low so that longer reaction times are ordinarily required for these volatile halides.

Certain higher boiling aliphatic halides may also be used when alkalies are employed. These include, for example, propylene dichloride and n-butyl chloride. The former boils at 96.8 C. at atmospheric pressure but steam distills from an aqueous solution substantially completely while propylene diamine which boils at 120 C. is largely retained in the aqueous solution. In like manner, n-butyl chloride and n-butyl amine boil at 77.5 C. and 77 C. respectively, but the former is readily volatilized with water vapor while the n-butyl amine has a relatively low vapor pressure in aqueous solution.

Certain other aliphatic halides which are useful in the process of the present invention have boiling points whichare too high to allow the use of alkali. These halides which include trimethylene chloride, ethyl bromide, methyl iodide, cyclopropyl chloride and the like may be steam distilled from an aqueous solution containing an amine hydrohalide and are, therefore, useful in the modification of the present invention in which no alkali is employed.

Although the process of the present invention is'generally applicable to the preparation of any organic pri- 7 mary amine by the reaction of a suitable halide and ammonia, it is generally used for the preparation of aliphatic primary amines. aromatic nuclei are usually too unreactive to make the preparation of primary aromatic amines feasible by the method of this invention. Further, aromatic compounds containing halogen atoms sutficiently reactive because of their position in aliphatic side chains or due to the presence of activating nuclear substituents are also unsuitable since these compounds are usually too high boiling for use in an aqueous system. On the other hand, although most fluorocarbons are insufliciently reactive for conversion by the present process, such compounds containing a more reactive halogenatom may be used with advantage. For example, 2,2,2-trifiuoro-l-chloroethane yields 2,2,2-trifluoroethylamine.

The'invention will be further illustrated by reference to the attached flow sheet.

Ethylene dichloride, water and ammonia are introduced by

lines

11, 12 and 13 respectively to fractionating tower 14 which maybe of the bubble cap or packed type. Recycle ammonia, if used, is also introduced to the tower at one or many points by line 15. The heat of reaction generated in the tower serves to evaporate ammonia and ethylene dichloride which are fractionated, ammonia passing overhead via line 16 and ethylene dichloride remaining in the mid-portion of the tower. Ammonia is liquefied in cooler 17 and either totally or partly returned to the. tower as reflux by line 18. The remaining ammonia flows through line-19 controlled by valve 20 to surge tank 21 and is recycled to the tower via line 15. The ratio of ammonia used for reflux and for recycle is controlled by valve 20. Water and ethylene diamine dihydrochloride pass downwardly in the tower vaporizing Halogen atoms attached directly to ethylene dichloride therefrom and returning it to the midportion of the tower. The bottoms, free of ammonia and ethylene dichloride, are removed through line 22 and in part pass by line 23 to reboiler 24, returning vapors by line 25 to the bottom of the tower. The product, ethylene diamine dihydrochloride in aqueous solution, is removed by line 26.

In the alternative procedure in which the base is liberated by means of caustic soda, the latter may be charged in aqueous solution by a line 27 entering the tower 14 at a point below the inlet line 13 for make-up ammonia. The bottoms product then comprises an aqueous solution of sodium chloride and ethylene diamine from which the latter may be recovered in any known manner.

The invention will be further illustrated by reference to the following example:

In an operation similar to that shown in the attached figure, with the exception that the inlet lines to the tower are modified by vertical adjustment thereof and in which the tower is about 35 feet in height and 0.25 square feet in cross-sectional area, 100 pounds per hour of ethylene dichloride is charged through a line entering the fractionating tower just below the top plate. Fresh anhydrous ammonia enters the tower at the rate of 35 pounds per hour through a line located about one-third of the distance above the bottom of the fractionating tower. A line located about one-fifth of the height of the column from the bottom carries 200 pounds per hour of 40% caustic. A line located at about the level of the second plate from the top of the fractionating tower carries 315 pounds per hour of additional water. Heat is supplied by the reaction of the ethylene dichloride, ammonia and caustic in the fractionating tower and additional heat is introduced in the reboiler. The liquid and vapor in equilibrium on the top plate are substantially anhydrous ammonia. Under a pressure of 225 p. s. i. g., ammonia gas is removed from the top of the tower at about 38 C. It is taken overhead at a rate of about 568 pounds per hour to the cooler which reduces the temperature of the liquid to about 35 C. About half of the ammonia is returned to the top plate of the tower as reflux and about half is returned through a surge tank to the reaction zone of the tower at about the mid-point thereof. The ratio of ammonia to ethylene dichloride is about 33:1. The liquid level in the bottom of the tower is just suflicient to maintain liquid feed to the reboiler. The bottoms leave the tower at a temperature of about 140 C. and comprise an aqueous solution of about 9% of ethylene diamine and 18% of sodium chloride. Ethylene diamine can be separated therefrom by distillation or other suitable means.

I claim:

1. A process for the production of primary aliphatic amines in which the formation of undesirable by-product amine compounds is substantially suppressed which comprises reacting an aliphatic halide which forms a water azeotrope boiling in the range extending from the boiling point of ammonia to the boiling point of water with ammonia in the central portion of a vertical reaction zone, charging water to said zone at a point above the central portion thereof whereby the primary aliphatic amine hydrohalide reaction product is dissolved and removed as an aqueous solution from the central portion to the lower portion of said zone, distilling dissolved reactant ammonia and aliphatic halide from said aqueous solution in the lower portion of said zone, thus returning reactants to the central portion of said zone, refluxing ammonia in the upper portion of said zone, and recovering an aqueous primary aliphatic amine hydrohalide solution from the lower portion of said zone.

2. A process for the production of primary aliphatic amines in which the formation of undesirable by-product amine compounds is substantially suppressed which comprises reacting an aliphatic halide with ammonia in the central portion of a vertical reaction zone, the water azeotrope of said aliphatic halide having a boiling point which is less than the boiling point of the water azeotrope of the primary aliphatic amine corresponding to said aliphatic halide and less than the boiling point of water but greater than the boiling point of ammonia, charging water to said zone at a point above the central portion thereof whereby the primary aliphatic amine hydrohalide reaction product is dissolved and removed as an aqueous solution from the central portion to the lower portion of said zone, charging a water soluble non-volatile alkali to the reaction zone below the central portion of said zone at a point where said alkali will not come in contact with substantial concentrations of the reactants thus converting said hydrohalide reaction product in said aqueous solution in the lower portion of said zone to the free amine, distilling dissolved reactant ammonia and aliphatic halide from said aqueous solution in the lower portion of said zone, thus returning reactants to the central portion of said zone, refluxing ammonia in the upper portion of said zone, and recovering an aqueous primary aliphatic amine solution from the lower portion of said zone.

3. The process of claim 2 in which the water soluble non-volatile alkali is sodium hydroxide.

4. A process for the production of ethylene diamine in which the formation of undesirable by-product amine compounds is substantially suppressed which comprises reacting ethylene dichloride with ammonia in the central portion of a vertical reaction zone, charging water to said zone at a point above the central portion thereof whereby the ethylene diamine dihydrochloride reaction product is dissolved and removed as an aqueous solution from the central portion to the lower portion of said zone, distilling dissolved reactant ammonia and ethylene dichloride from said aqueous solution in the lower portion of said zone thus returning reactants to the central portion of said zone, and recovering an aqueous solution of ethylene diamine dihydrochloride from the lower portion of said zone.

5. A process for the production of ethylene diamine in which the formation of undesirable by-product amine compounds is substantially suppressed which comprises reacting ethylene dichloride with ammonia in the central portion of a vertical reaction zone, charging water to said zone at a point above the central portion thereof whereby the ethylene diamine dihydrochloride reaction product is dissolved and removed as an aqueous solution from the central portion to the lower portion of said zone, charging a water soluble non-volatile alkali to the reaction zone below the central portion of said zone at a point where the alkali will not come in contact with substantial concentrations of the reactants thus converting said ethylene diamine dihydrohalide reaction product in said aqueous solution in the lower portion of said zone to the free amine, distilling dissolved reactant ammonia and ethylene dichloride from said aqueous solution in the lower portion of said zone thus returning reactants to the central portion of said zone, and recovering an aqueous solution of ethylene diamine from the lower portion of said zone.

6. The process of claim 5 in which the water soluble non-volatile alkali is sodium hydroxide.

References Cited in the file of this patent UNITED STATES PATENTS 1,832,534 Curme, Jr. et al. Nov. 17, 1931

Claims

1. A PROCESS FOR THE PRODUCTION OF PRIMARY ALIPHATIC AMINES IN WHICH THE FORMATION OF UNDESIRABLE BY-PRODUCT AMINE COMPOUNDS IS SUBSTANTIALLY SUPPRESSED WHICH COMPRISES REACTING AN ALIPHATIC HALIDE WHICH FORMS A WATER AZETROPE BOILING IN THE RANGE EXTENDING FROM THE BOILING POINT OF AMMONIA TO THE BOILING POINT OF WATER WITH AMMONIA IN THE CENTRAL PORTION OF A VERTICAL REACTION ZONE, CHARGING WATER TO SAID ZONE AT A POINT ABOVE THE CENTRAL PORTION THEREOF WHEREBY THE PRIMARY ALIPHATIC AMINE HYDROHALIDE REACTION PRODUCT IS DISSOLVED AND REMOVED AS AN AQUEOUS SOLUTION FROM THE CENTRAL PORTION TO THE LOWER PORTION OF SAID ZONE, DISTILLING DISSOLVED REACTANT AMMONIA AND ALIPHATIC HALIDE FROM SAID AQUEOUS SOLUTION IN THE LOWER PORTION OF SAID ZONE, THUS RETURNING RECTANTS TO THE CENTRAL PORTION OF SAID ZONE, REFLUXING AMMONIA IN THE UPPER PORTION OF SAID ZONE, AND RECOVERING AN AQUEOUS PRIMARY ALIPHATIC AMINE HYDROHALIDE SOLUTIN FROM THE LOWER PORTION OF SAID ZONE.